EP1828308B1 - Compositions de polyoxymethylene haute densite - Google Patents

Compositions de polyoxymethylene haute densite Download PDF

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Publication number
EP1828308B1
EP1828308B1 EP05851955A EP05851955A EP1828308B1 EP 1828308 B1 EP1828308 B1 EP 1828308B1 EP 05851955 A EP05851955 A EP 05851955A EP 05851955 A EP05851955 A EP 05851955A EP 1828308 B1 EP1828308 B1 EP 1828308B1
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Prior art keywords
composition
weight percent
groups
polymer
mineral
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EP05851955A
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German (de)
English (en)
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EP1828308A2 (fr
Inventor
Shengmei Yuan
Edmund A. Flexman
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority claimed from PCT/US2005/042199 external-priority patent/WO2006057975A2/fr
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Definitions

  • Polymeric materials in general are useful for preparing a wide variety of articles, including those with intricate shapes, and permit considerable flexibility in the design of the articles.
  • most polymers have lower density than other commonly-used materials such as metals or ceramics, and despite the greater design flexibility offered by polymeric materials, they are frequently unsuitable for applications where a high density material is required. Such applications are often in the area of aesthetics where a polymeric article with the heft and feel of metal or ceramic is desired.
  • High density polymeric materials have been prepared by adding high density metal powders and/or metal salts to polymeric materials.
  • European published patent application 0 423 510 discloses the use of one or more of barium sulfate, zinc oxide, zirconium oxide, and zirconium silicate in a wide variety of thermoplastic resins, including acetals.
  • Polyoxymethylene also known as polyacetal
  • Polyacetal has excellent physical properties such as toughness and stiffness, a low coefficient of friction, good solvent resistance, and the ability to crystallize rapidly, making polyoxymethylene resin compositions useful for preparing articles for use in many demanding applications.
  • polyoxymethylene is sensitive to degradation and tends to discolor and degrade, often unpredictably, in the presence of many common high density additives.
  • a polyoxymethylene composition comprising:
  • an article made from the polyoxymethylene composition above includes casino or poker chips and perfume bottle caps.
  • the present invention is a high density polyoxymethylene composition
  • a high density polyoxymethylene composition comprising at least one polyoxymethylene, at least one surface-coated mineral selected from zinc oxide, barium sulfate, and titanium dioxide; and at least one thermal stabilizer.
  • the polyoxymethylene (i.e. POM or polyacetal) used in the present invention can be one or more homopolymers, copolymers, or a mixture thereof.
  • Homopolymers are prepared by polymerizing formaldehyde and/or formaldehyde equivalents, such as cyclic oligomers of formaldehyde.
  • Copolymers are derived from one or more comonomers generally used in preparing polyoxymethylene compositions in addition to formaldehyde and/ formaldehyde equivalents. Commonly used comonomers include acetals and cyclic ethers that lead to the incorporation into the polymer chain of ether units with 2-12 sequential carbon atoms.
  • the quantity of comonomer will not be more than 20 weight percent, preferably not more than 15 weight percent, and most preferably about two weight percent.
  • Preferable comonomers are 1,3-dioxolane, ethylene oxide, and butylene oxide, where 1,3-dioxolane is more preferred, and preferable polyoxymethylene copolymers are copolymers where the quantity of comonomer is about 2 weight percent.
  • the homo- and copolymers are: 1) homopolymers whose terminal hydroxy groups are end-capped by a chemical reaction to form ester or ether groups; or, 2) copolymers that are not completely end-capped, but that have some free hydroxy ends from the comonomer unit or are terminated with ether groups.
  • Preferred end groups for homopolymers are acetate and methoxy and preferred end groups for copolymers are hydroxy and methoxy.
  • the polyoxymethylenes used in the compositions of the present invention can be branched or linear and will generally have a number average molecular weight of at least 10,000, and preferably about 20,000 to about 90,000.
  • the molecular weight can be conveniently measured by gel permeation chromatography in m-cresol at 160 °C using a DuPont PSM bimodal column kit with nominal pore size of 60 and 1000 ⁇ .
  • the molecular weight can also be measured by determining the melt flow using ASTM D1238 or ISO 1133.
  • the melt flow will preferably be in the range of 0.1 to 100 g/min, more preferably from 0.5 to 60 g/min, or yet more preferably from 0.8 to 40 glmin. for injection molding purpose.
  • the polyoxymethylene will be present in the composition in 20 to 70 weight percent, or preferably in 35 to 70 weight percent, or more preferably 45 to 70 weight percent, based on the total weight of the composition.
  • the composition will contain a surface-coated mineral comprising a mineral selected from one or more of zinc oxide, barium sulfate, and titanium dioxide.
  • Preferred coating agents include one or more of fatty acids, fatty acid salts, fatty acid esters, and fatty acid amides. Suitable coating agents may also include polymeric materials.
  • fatty acid is meant a straight chain or branched aliphatic acid having between 10 and 40 carbons atoms, inclusive.
  • Fatty acid esters may be monoesters, diesters, triesters, or higher esters.
  • the fatty acids, fatty acid salts, fatty acid esters, and fatty acid amides may be saturated or unsaturated.
  • Unsaturated fatty acids, salts, esters, and amides that have been fully or partially epoxidized may be used.
  • suitable surface coating agents include glycerol monostearate, glycerol monooleate, stearic acid, calcium stearate, linseed oil, soybean oil, and epoxidized soybean oil.
  • the coated mineral preferably comprises about 95 to about 99.5 weight percent, or more preferably about 97 to about 99 weight percent mineral and preferably about 0.5 to 5 weight percent, or more preferably about 1 to about 3 weight percent coating agent.
  • the coating agent may be applied to the mineral using any method known in the art such as tumbling the mineral and coating agent in a mixer.
  • the coated mineral will be present in 20 to 70 weight percent, or preferably in 40 to 70 weight percent, or more preferably 40 to 70 weight percent based on the total weight of the composition.
  • the composition of the present invention contains at least one thermal stabilizer that serves to stabilize the polymer from decomposition and reduce the amount of formaldehyde emitted from the composition and articles made therefrom.
  • the stabilizer is preferably one or more of a polymer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain; a polyamide; a hydroxy containing polymer or oligomer, or a polymer having epoxy groups as pendant groups.
  • the polymeric stabilizer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain used in the present invention is described in U.S. patent 5,011,890 , which is hereby incorporated by reference.
  • the polymeric stabilizer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain can be a homopolymer or copolymer.
  • “formaldehyde reactive nitrogen groups” is meant pendant groups on the polymer chain that contain a nitrogen bonded to one or, preferably, two hydrogen atoms.
  • the polymeric stabilizer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain preferably has at least ten repeat units. It preferably has a weight average molecular weight of greater than 5,000, more preferably greater than 10,000.
  • the formaldehyde reactive nitrogen groups can be incorporated into the polymeric stabilizer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain by using an appropriate nitrogen containing monomer, such as, for example, acrylamide and methacrylamide.
  • Preferred nitrogen-containing monomers are those that result in polymeric stabilizer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain having two hydrogen atoms attached to the nitrogen.
  • the formaldehyde reactive nitrogen groups can be generated on the polymeric stabilizer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain by modification of the polymer or copolymer.
  • the quantity of the formaldehyde reactive nitrogen groups in polymeric stabilizer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain is preferably such that the atoms in the backbone to which the formaldehyde reactive groups are attached, either directly or indirectly, are separated from each other (i.e., connected to each other) by not more than twenty chain atoms.
  • the polymeric stabilizer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain will contain at least one formaldehyde reactive nitrogen group per each twenty carbon atoms in the backbone of the polymer. More preferably, the ratio of formaldehyde reactive nitrogen groups to carbon atoms in the backbone will be 1:2-1:10 and yet more preferably 1:2-1:5.
  • the polymeric stabilizer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain can be a homopolymer or a copolymer. It is preferred that the polymeric stabilizer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain be polymerized from acrylamide or methacrylamide monomer by free radical polymerization and that the polymeric stabilizer prepared therefrom consist of at least 75 mole percent of units derived from acrylamide or methacylamide. More preferably, it consists of at least 90 mole percent of the above units, even more preferably, it consists of at least 95 mole percent of the above units, and yet more preferably, it consists of at least 99 mole percent of the above unit.
  • the polymeric stabilizer having formaldehyde reactive nitrogen groups as pendant groups on the polymer chain may be a copolymer in that it is polymerized from more than one monomer.
  • the comonomer may or may not contain formaldehyde reactive nitrogen groups. Examples of other monomers that may be thus incorporated include styrene, ethylene, alkyl acrylates, alkyl methacrylates,N-vinylpyrrolidone, and acrylonitrile.
  • the comonomer preferably should be added such that it does not unduly minimize the number of moles of formaldehyde reactive groups per gram of polymeric stabilizer. Further, it should not unduly minimize the number of formaldehyde reactive sites per gram of polymeric stabilizer.
  • Specific preferred stabilizers that are copolymeric include copolymers of hydroxypropyl methacrylate with acrylamide, methacrylamide, or dimethylaminoethyl methacrylate.
  • the polyamide stabilizer is an aliphatic polyamide and can include polyamide 6 and polyamide 6,6 and copolyamides such as polyamide 6/6,12 and polyamide 6/6,6 and terpolyamides such as polyamide 6,6/6,10/6.
  • the polyamide stabilizer preferably has a melting point of less than about 210 °C.
  • the polyamide stabilizer may be predispersed in a carrier resin such an ethylene/methacrylic acid copolymer, a partially neutralized ethylene/methacrylic acid copolymer (e.g. ionomer), or a thermoplastic polyurethane.
  • Hydroxy containing polymers and oligomers are described in U.S. patent 4,766,168 , which is hereby incorporated by reference.
  • the hydroxy groups of the hydroxy-containing polymers and oligomers used may be directly bonded to the polymer or oligomer backbone, or may be present on pendant groups, or both.
  • the hydroxy containing polymers and oligomers will contain on average at least one hydroxy group per each 20 carbon atoms in the polymer or oligomer backbone and not more than one hydroxy group per carbon atom in the backbone.
  • Suitable hydroxy containing polymers and oligomers include ethylene/vinyl alcohol copolymer; poly(vinyl alcohol); vinyl alcohol/methylmethacrylate copolymers; and hydroxyesters of poly(meth)acrylates.
  • Suitable examples of polymers having epoxy groups as pendant groups include polymers having glycidyl groups, such as polymers formed by polymerizing glycidyl methacrylate with ethylene and an acrylic ester or methacrylic ester.
  • An examples of a suitable acrylic ester includes butyl acrylate.
  • a preferred polymer having epoxy groups as pendant groups is an ethylene/n-butyl acrylate/glycidyl methacrylate terpolymer, commonly referred to as EBAGMA.
  • the thermal stabilizer is preferably present in about 0.05 to about 4 weight percent, or more preferably in about 0.1 to about 1 weight percent, based on the total weight of the composition.
  • compositions of the present invention will preferably have a density of at least about 1.6 g/cc, more preferably of at least about 2 g/cc, or yet more preferably of at least 2.3 g/cc.
  • compositions of the present invention may optionally further comprise additional components such as about 10 to about 40 weight percent impact modifiers; about 0.1 to about 1 weight percent lubricants; about 0.5 to about 5 weight percent plasticizer; about 0.01 to about 2 weight percent antioxidants; about 3 to about 40 weight percent fillers; about 1 to about 40 weight percent reinforcing agents; about 0.5 to about 10 weight percent nanoclays; about 0.01 to about 3 weight percent thermal stabilizers; about 0.05 to about 2 weight percent ultraviolet light stabilizers; about 0.05 to about 3 weight percent nucleating agents; and/or about 0.2 to about 5 weight percent flame retardants, where all weight percentages are based on the total weight of the composition.
  • additional components such as about 10 to about 40 weight percent impact modifiers; about 0.1 to about 1 weight percent lubricants; about 0.5 to about 5 weight percent plasticizer; about 0.01 to about 2 weight percent antioxidants; about 3 to about 40 weight percent fillers; about 1 to about 40 weight percent reinforcing agents; about 0.5 to about 10 weight percent nanoclays;
  • suitable fillers include glass fibers and minerals such as precipitated calcium carbonate, talc, and wollastonite.
  • suitable impact modifiers include thermoplastic polyurethanes, polyester polyether elastomers, and core-shell acrylate polymers.
  • lubricants include silicone lubricants such as dimethylpolysiloxanes and their derivatives; oleic acid amides; alkyl acid amides; bis-fatty acid amides such as N,N'-ethylenebisstearamide; non-ionic surfactant lubricants; hydrocarbon waxes; chlorohydrocarbons; fluorocarbons; oxy-fatty acids; esters such as lower alcohol esters of fatty acids; polyvalent alcohols such as polyglycols and polyglycerols; and metal salts of fatty acids such as lauric acid and stearic acid.
  • nucleating agents include titanium oxides and talc.
  • Preferred antioxidants are hindered phenol antioxidants such as Irganox® 245 and 1090 available from Ciba.
  • thermal stabilizers include calcium carbonate, magnesium carbonate, and calcium stearate.
  • ultraviolet light stabilizers include benzotriazoles, benzophenones, aromatic benzoates, cyano acrylates, and oxalic acid anilides.
  • the high-density polyoxymethylene compositions of the present invention are made by melt-blending the components using any known methods.
  • the component materials may be mixed thoroughly using a melt-mixer such as a single or twin-screw extruder, blender, kneader, Banbury mixer, etc. to give a resin composition.
  • a melt-mixer such as a single or twin-screw extruder, blender, kneader, Banbury mixer, etc.
  • part of the materials may be mixed in a melt-mixer, and the rest of the materials may then be added and further thoroughly melt-mixed.
  • compositions of the present invention may be molded into articles using any suitable melt-processing technique. Commonly used melt-molding methods known in the art such as injection molding, extrusion molding, blow molding, and injection blow molding are preferred and injection molding is more preferred.
  • the compositions of the present invention may be formed into films and sheets by extrusion to prepare both cast and blown films. These sheets may be further thermoformed into articles and structures that may be oriented from the melt or at a later stage in the processing of the composition.
  • compositions of the present invention examples include poker and casino chips, perfume bottle caps, and consumer products where the heft and feel of metal are needed.
  • the minerals were coated with 2 weight percent, based on the weight of the mineral and coating agent, as indicated in Tables 1 and 2 by blending the mineral and coating agent in a Welex Laborotory Mixer manufactured by Welex Corporation, Philadelphia, PA at medium mixing speed. Coating was done at room temperature with epoxidized soybean oil. The mixer was heated to about 70 °C with hot water when stearic acid and glyceryl monostearate were used.
  • the thermal stability of the compositions was determined by heating pellets of the compositions for about 30 minutes at a temperature of 259 °C.
  • the formaldehyde evolved during the heating step is swept by a stream of nitrogen into a titration vessel containing a sodium sulfite solution where it reacts with the sodium sulfite to generate sodium hydroxide.
  • the generated sodium hydroxide is continuously titrated with hydrochloric acid to maintain the original pH.
  • the total volume of acid used is plotted as a function of time.
  • the total volume of acid consumed at 30 minutes is proportional to the formaldehyde generated by the heated polyoxymethylene and is a quantitative measure of thermal stability.
  • melt flow index (MFR) was measured for each sample at 190 °C and at a load of 2.16 kg using ASTM-D 1238 method. The results are shown in Table 1.
  • the ingredients shown in Tables 1 and 2 were compounded using a 72.2-cm(30-inch) Wemer & Pfleiderer ZSK-30 twin-screw extruder.
  • the blends were compounded at a barrel temperature of about 190-210 °C, a screw speed of about 150 RPM screw speed, and a rate of about 13.6 kg (30 pounds) per hour.
  • the compositions were cooled and pelletized.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine polyoxyméthylène haute densité, comprenant du polyoxyméthylène; au moins un minéral enrobé sélectionné parmi l'oxyde de zinc, le sulfate de baryum et le dioxyde de titane, ainsi qu'au moins un stabilisateur thermique.

Claims (13)

  1. Composition de polyoxyméthylène, comprenant:
    (a) 20 à 70 pour cent en poids de polyoxyméthylène,
    (b) 20 à 70 pour cent en poids d'au moins un minéral revêtu en surface, le minéral étant sélectionné dans le groupe constitué de l'oxyde de zinc, du dioxyde de titane, et du sulfate de barium,
    (c) 0,05 à 4 pour cent en poids d'au moins un stabilisateur thermique, et optionnellement
    (d) 10 à 40 pour cent en poids de modificateurs d'impact.
  2. Composition selon la revendication 1, dans laquelle le stabilisateur thermique est un polymère ayant des groupes d'azote réagissant avec le formaldéhyde en tant que groupes pendants sur la chaîne polymère et/ou un polyamide et/ou un polymère ou oligomère contenant de l'hydroxy et/ou un polymère ayant des groupes epoxy en tant que groupes pendants.
  3. Composition selon la revendication 1 ou 2, dans laquelle le minéral est revêtu d'un ou de plusieurs agents de revêtement sélectionnés parmi les acides gras, les sels d'acides gras, les esters d'acides gras, et les amides d'acides gras, de préférence d'un ou plusieurs agents sélectionnés parmi l'acide stéarique, des esters d'acide stéarique, des sels d'acide stéarique, de l'huile de lin, de l'huile de soja, et de l'huile de soja époxydée, de manière la plus préférée de monostéarate de glycérol et/ou de stéarate de calcium.
  4. Composition selon la revendication 1, 2 ou 3, dans laquelle le stabilisateur thermique est un polymère ayant des groupes d'azote réagissant avec le formaldéhyde en tant que groupes pendants sur la chaîne polymère, de préférence un polyacrylamide ou un polyméthacrylamide.
  5. Composition selon la revendication 1, 2 ou 3, dans laquelle le stabilisateur thermique est un polymère ou oligomère contenant de l'hydroxy, de préférence un copolymère d'éthylène/alcool vinylique.
  6. Composition selon la revendication 1, 2 ou 3, dans laquelle le stabilisateur thermique est un polymère ayant des groupes epoxy en tant que groupes pendants, de préférence un terpolymère d'éthylène/butylacrylate/glycidyl/méthacrylate.
  7. Composition selon l'une quelconque des revendications 1 à 6, dans laquelle le minéral est l'oxyde de zinc.
  8. Composition selon l'une quelconque des revendications 1 à 6, dans laquelle le minéral est le sulfate de baryum
  9. Composition selon l'une quelconque des revendications 1 à 6, dans laquelle le minéral est le dioxyde de titane.
  10. Composition selon l'une quelconque des revendications 1 à 9, la composition ayant une densité d'au moins 2,3 g/cm3, de préférence au moins 2g/cm3, mieux encore d'au moins 1,6 g/cm3.
  11. Article fabriqué à partir de la composition selon l'une quelconque des revendications 1 à 10.
  12. Article selon la revendication 11, sous la forme d'un jeton de casino ou de poker.
  13. Article selon la revendication 12, sous la forme d'un bouchon de bouteille de parfum.
EP05851955A 2004-11-23 2005-11-18 Compositions de polyoxymethylene haute densite Expired - Fee Related EP1828308B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US63070404P 2004-11-23 2004-11-23
PCT/US2005/042199 WO2006057975A2 (fr) 2004-11-23 2005-11-18 Compositions de polyoxymethylene haute densite

Publications (2)

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EP1828308A2 EP1828308A2 (fr) 2007-09-05
EP1828308B1 true EP1828308B1 (fr) 2012-01-04

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CN (1) CN101061178A (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8436077B2 (en) * 2009-12-16 2013-05-07 Cristal Usa Inc. Lipid-treated particles and polymers containing the particles
CN103819868B (zh) * 2012-11-19 2018-03-06 合肥杰事杰新材料股份有限公司 一种汽车惯性盘用聚甲醛材料及其制备方法和用途
WO2016104255A1 (fr) * 2014-12-22 2016-06-30 三菱瓦斯化学株式会社 Composition de résine polyacétalique et article moulé obtenu à partir de ladite composition

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CN101061178A (zh) 2007-10-24

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